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DOI 10.1007/s10973-011-1474-0
123
M. C. D. Silva et al.
studied. We also use the gas chromatography technique for column utilized was a Durabond-DB-23 (Agilent Technol-
supplementary characterization of winterized fractions. ogies) and a He flow of 3 mL min-1 was used as entrain-
ment gas. The fat acids characterization was performed by
comparison with the software Mass Spectral Database
Experimental procedure NIST/EPA/NIH standard.
123
Study of ethylic Babassu biodiesel properties
0
of DSC cooling curve. The Pc were assigned to each
EBBS #2
cooling curve, based on the temperature at which the
greatest value for the heat flow occurred, while Tf were
–4 EBBS # 1 assigned to each heating curve, based on the temperature at
Heating flow/mW
EBB which the lowest value for the heat flow occurred. Table 1
shows the respective values of Tc, Pc, and Tf. The winter-
–8 EBBL
ization process do not changes the freezing point and the
melting temperature of the different fractions of winter-
Endo
ized. Also the start of the crystallization does not decrease
–12
significantly with the winterization process, both the solid
(EBBS#1) and the liquid (EBBL) fractions present similar
–16
values of Tc and the difference of 2.4 °C observed between
EBBL and EBBS#2 possible can the be attributed to the
–40 –20 0 20 40
o
differences in the physics properties of this two fractions,
Temperature/ C this is to EBBL the crystallization occurs between the
Fig. 2 DSC heating curves obtained for the ethylic Babassu biodiesel
liquid to solid state, whereas for EBBS#2 it occurs between
and for the respective fractions of the winterized sample. Curve like-gel to solid state.
offsets on the y-axis: -7.8, -5.8, and -2.58/mW for EBBL, EBB, Using gas chromatography CG-MS, we determine the
and EBBS#1, respectively fat acid ethyl esters amounts of the winterized EBBL,
EBBS#1, and EBBS#2 samples compared with the non-
Table 1 Temperatures observed in the DSC curves (cooling and winterized ethylic Babassu biodiesel (showed in Table 2).
heating) The analysis for EBB shows saturated compositions
Sample Tc/°C Pc/°C Tf/°C (97.2%), unsaturated (2.6%), and non identified fat acid
trace (*0.2%). The concentration of saturation and unsat-
EBB -8.6 -28.8 -13.5 uration not change significantly to the EBBL, EBBS#1, and
EBBL -10.1 -28.7 -12.6 EBBS#2 samples. This result shows a very large predom-
EBBS#1 -9.8 -28.5 -13.2 inance of esters from saturated fat acid in the ethylic
EBBS#2 -7.7 -28.4 -14.0 Babassu biodiesel and because of this, the winterization
process does not provoke significantly changes in the
However for the EBBS#2, the main peak can be associated respective fractions of winterized sample.
with a transition from solid to like-gel phase and a second Figure 3 shows the X-ray diffraction pattern as a func-
peak correspond to transition from like-gel to liquid phase. tion of temperature for ethylic Babassu biodiesel. We see
The start of crystallization temperature (Tc), freezing through the diffraction peak widths (full width at half
point (Pc), and the melt temperature (Tf) were obtained maximum) that the sample becomes more crystalline as the
using the DSC data. Tc was taken as the onset point of the temperature decreases and the crystallization process
transition, which is the point at which the extrapolated beginning around -8 °C, where the small diffraction peak
baseline intersects the extrapolated slop in the higher peak can be observed.
Table 2 Gas chromatography results for winterized fractions and nonwinterized ethylic Babassu biodiesel
Samples C8:0/% C10:0/% C12:0/% C14:0/% C16:0/% C18:0/% C18:1n-9/% C18:2n-6/%
caprilic capric lauric miristic palmitic stearic oleic linoleic
123
M. C. D. Silva et al.
EBB EBBS #1
Intensity/a.u.
T = –50 °C
T = –50 °C –30 °C
–30 °C –20 °C
Intensity/a.u.
–20 °C –10 °C
–10 °C –8 °C
–8 °C
EBBS #2
18 20 22 24 26
2θ /°
18 20 22 24 26
2θ /°
Intensity/a.u.
Fig. 5 X-ray diffraction (XRD) for the solid and like-gel fraction of
winterized ethylic Babassu biodiesel, EBBS#1 (top) and EBBS#2
(bottom). The measurements were performed in a sequence of heating
the sample
T = –50 °C
–30 °C
–20 °C Conclusions
–10 °C
18 20 22 24 26
The physical–chemical properties of ethylic Babassu bio-
2θ /° diesel obtained in this work attend the specifications
required by national (ANP) and international (ASTM and
Fig. 4 X-ray diffraction (XRD) for the liquid fraction of winterized EN) standards.
ethylic Babassu biodiesel (EBBL), obtained at -50, -30, -20 and Measurements of DSC and X-ray diffraction were used
-10 °C. The measurements were performed in a sequence of heating
the sample to evaluate the low temperature properties of Babassu
biodiesel. Both techniques agree with the crystallization of
Babassu biodiesel occurs around -8 °C, i.e., the ethyl
Figures 4 and 5 show the X-ray diffraction pattern as a esters from saturated fat acid suffer nucleation and form
function of temperature for EBBL, EBBS#1, and EBBS#2, crystals resulting in the solidification of biodiesel.
respectively. Both solid fractions and the liquid fraction of The Babassu biodiesel was submitted to a winterization
the winterized biodiesel present the same begins of crystal process at low temperature and three distinct fractions
nucleation temperature observed in the EBB. (liquid phase, solid phase, and like-gel phase) were
These results are in agreement with the DSC experi- obtained. The characterization of low temperatures prop-
ments in which the star of crystallization temperature was erties shows that the start of crystallization temperature
estimated around to -8 °C. For EBBS#2 we performed remains unaltered for all winterized fractions. On the other
X-ray diffraction measurements up to 25 °C and indeed the hand, to EBBS#2 the transition from like-gel phase to
crystallization peaks appears only below -8 °C, indicating liquid phase occurs only around 20 °C. Our results indicate
that the phase transition observed around 20 °C in DSC not change in Babassu biodiesel crystallization temperature
curve is characteristic of a glass transition. with winterization process. The higher concentrations of
123
Study of ethylic Babassu biodiesel properties
ethyl esters from saturated fat acid are probably responsible 8. Santos NA, Tavares MLA, Rosenhaim R, Silva FC, Fernandes
for this characteristic of ethylic Babassu biodiesel. VJ, Santos IMG, Souza AG. Thermogravimetric and calorimetric
evaluation of Babassu biodiesel obtained by the methanol route.
The X-ray diffraction, combined with DSC measure- J Therm Anal Calorim. 2007;87:649–52.
ments, was efficiently employed to the monitoring of 9. Stournas S, Lois E, Serdari A. Effects of fatty acid derivatives on
Babassu biodiesel crystallization process and for the elu- the ignition quality and cold flow of diesel fuel. J Am Oil Chem
cidation of the like-gel fraction nature as an amorphous Soc. 1995;72:433–7.
10. Dunn RO, Shockley MW, Bagby MO. Improving the low tem-
phase. These techniques are very helpful technique in the perature flow properties of alternative diesel fuels: vegetable oil-
characterization of cold-flow biodiesel properties. derived methyl esters. J Am Oil Chem Soc. 1996;73:1719–28.
11. Dunn RO, Bagby MO. Low-temperature properties of triglyceride-
Acknowledgements The authors would like to thank the Brazilian based diesel fuels: transesterified methyl esters and petroleum
Agencies FINEP, CNPq and FAPEMA for the financial support. middle distillate/ester blends. J Am Oil Chem Soc. 1995;72:
895–904.
12. Chen BS, Sun YQ, Fang JH, Wang J, Wu J. Effect of cold flow
improvers on flow properties of soybean biodiesel. Biomass
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